EP0311318B1

EP0311318B1 - Ashless lubricant compositions for internal combustion engines

Info

Publication number: EP0311318B1
Application number: EP88309139A
Authority: EP
Inventors: Glen Paul Fetterman, Jr.; Alan Alvin Schetelich
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 1987-10-02
Filing date: 1988-09-30
Publication date: 1992-01-15
Anticipated expiration: 2008-09-30
Also published as: BR8805084A; JPH01163294A; JP2780029B2; CA1327350C; DE3867791D1; AU2332788A; ES2027767T3; AU614546B2; EP0311318A1; AR246094A1

Description

This invention relates to lubricating oil compositions which exhibit marked reduction in engine carbon deposits. More particularly, this invention is directed to ashless lubricating oil compositions which are adapted for use in diesel engines and which contain ashless dispersants, sulfurized alkyl phenols and organo-sulfur anticorrosion agents.

BACKGROUND OF THE INVENTION

It is an objective of the industry to provide lubricating oil compositions which exhibit improvements in minimized engine deposits and low rates of lubricating oil consumption, particularly in diesel engine vehicles.
Among the conventionally used lubricating oil additives, zinc dihydrocarbyl dithiophosphates perform multiple functions in the motor oil, namely, oxidation inhibition, bearing corrosion inhibition, and extreme press- ure/antiwear protection for the valve train.
Early patents illustrated compositions using polyisobutenylsuccinimide dispersants in combination with zinc dialkyldithiophosphates which were employed in lubricating oil compositions with other conventional additives such as detergents, viscosity index improvers, rust inhibitors and the like. Typical of these early disclosures are U.S. Patents 3,018,247, 3,018,250 and 3,018,291.
Since phosphorus is a catalyst poison for catalytic converters, and since the zinc itself offers a source for sulfated ash, the art has sought to reduce or eliminate such zinc-phosphorus-containing motor oil components. Exemplary of prior art references directed to the reduction in phosphorus-containing lubricant additives are U.S. Patents 4,147,640 ; 4,330,420 ; and 4,639,324.
U.S. Patent 4,147,640 relates to lubricating oils having improved antioxidant and antiwear properties which are obtained by reacting an olefinic hydrocarbon having from 6 to 8 carbon atoms and about 1 to 3 olefinic double bonds concurrently with sulfur and hydrogen sulfide and thereafter reacting the resulting reaction intermediate with additional olefin hydrocarbon. These additives are disclosed to be generally used in conjunction with other conventional oil additives such as overbased metal detergents, polyisobutenylsuccinimide dispersants, and phenolic antioxidants. While it is disclosed that the amount of the zinc additive can be greatly reduced, giving a "low ash" or "no ash" lubricant formulation, it is apparent the patentee was referring to Zn-derived ash, and not total SASH levels.
U.S. Patent 4,330,420 relates to low ash, low phosphorus motor oils having improved oxidation stability as a result of the inclusion of synergistic amounts of dialkyldiphenylamine antioxidant and sulfurized polyolefin. It is disclosed that the synergism between these two additives compensates for the decreased amounts of phosphorus in the form of zinc dithiophosphate. The fully formulated motor oils are said to comprise 2 to 10 wt.% of ashless dispersant, 0.5 to 5 wt.% of recited magnesium or calcium detergent salts (to provide at least 0.1% of magnesium or calcium), from 0.5 to 2.0 wt.% of zinc dialkyldithiophosphate ; from 0.2 to 2.0 wt.% of a dial- kyldiphenolamine antioxidant; from 0.2 to 4 wt.% of a sulfurized polyolefin antioxidant; from 2 to 10 wt.% of a first, ethylene propylene VI improver ; from 2 to 10 wt.% of a second VI improver consisting of methacrylate terpolymer, and the balance baseoil.
U.S. Patent 4,639,324 discloses that metal dithiophosphate salts, while useful as antioxidants, are a source of ash, and discloses an ashless antioxidant comprising a reaction product made by reacting at least one aliphatic olefinically unsaturated hydrocarbon having from 8 to 36 carbons concurrently with sulfur and at least one fatty acid ester to obtain a reaction intermediate which is then reacted with additional sulfur and a dimer of cyclopentadiene or lower C₁ to C₄ alkyl substituted cyclopentadiene dimers. It is disclosed that these additives in lubricating compositions are generally used in conjunction with other conventional oil additives such as neutral and overbased calcium or magnesium alkaryl sulfonates, dispersants and phenolic antioxidants. It is disclosed that when using the additives of this invention, the amount of the zinc additive can be greatly reduced giving a "low ash" or "no ash" lubricant formulation. Again, it is apparent that the patentee was referring to Zn-derived ash, and not to total SASH.
Metal detergents have been heretofore employed in motor oils to assist in controlling varnish formation and corrosion, and to thereby minimizing the adverse impact which varnish and corrosion have upon the efficiency of an internal combustion engine by minimize the clogging of restricted openings and the reduction in the clearance of moving parts.
U.S. Patent 4,089,791 relates to low ash mineral lubricating oil compositions comprising a mineral oil base in minor amounts of an overbased alkaline earth metal compound, a zinc dihydrocarbyl dithiphosphate (ZDDP) and a substituted trialkanolamine compound, wherein at least 50% of the ZDDP compounds consists of zinc dialkaryl dithiophosphates, in order to provide a formulated motor oil which will pass the MS IIC Rust Test and the L-38 Bearing Weight Loss Test. The patent illustrates three oil formulations, containing overbased calcium detergent, ZDDP, trialkanolamine and unspecified conventional lubricating oil additives to provide viscosity index improvement, antioxidant, dispersant and anti-foaming properties. The illustrated formulations each had about 0.66 wt.% SASH levels, based on the reported Ca and Zn concentrations. No diesel motor oil formulations are illustrated.
U.S. Patent4,153,562 relates to antioxidants, which are disclosed to be particularly useful for compounded lubricating oils that are intended for heavy duty use in automotive crankcase formulations of relatively low ash content, wherein the antioxidants are prepared by the condensation of phosphorodithioates of alkylphenol sulfides with unsaturated compounds such as styrene. The antioxidants are exemplified at levels of from 0.3 to 1.25 wt.% in lube oil compositions (Example 3) which also contain about 2.65 wt.% (a.i.) borated polyisobutenyl-succinimide dispersant, about 0.06 wt.% Mg as overbased magnesium sulfonate detergent inhibitor, and about 0.10 wt.% Zn as zinc dialkyldithiophosphate antiwear agent (containing mixed CJC5 alkyl groups).
U.S. Patent 4,157,972 indicates that the trend to unleaded fuels and ashless lubricating compositions has necessitated the search for non-metallic (ashless) substitutes for metallo-organo detergents, and relates to tet- rahydropyrimidyl-substituted compounds which are disclosed to be useful as ashless bases and rust inhibitors. The Examples of the Patent compare the performance of various lubricating oil formulations in a Ford V8 varnish test (Table I) and additional formulations, which are named as either "low-ash" or "ashless", in a Humidity Cabinet Rust Test (Table II). The SASH levels of the "low ash" formulations are not reported and cannot be determined from the information given for the metal detergent - and ZDDP - components.
U.S. Patent 4,165,292 discloses that overbased metal compounds provide effective rust inhibition in automotive crankcase lubricants and that in the absence of overbased additives, as in ashless oils, or when such additives are present in reduced amounts, as in "low ash" oils, rusting becomes a serious problem. Such rust requirements are evaluated by ASTM Sequence IIC engine-tests. The Patent discloses a non-ash forming corrosion or rust inhibitor comprising a combination of an oil-soluble basic organic nitrogen compound (having a recited basicity value) and an alkenyl or alkyl substituted succinic acid having from 12 to 50 carbon atoms. The basic organic nitrogen compound and the carboxylic acid compound are required to be used together to achieve the desired rust-inhibiting properties. It is disclosed that best results are achieved by use of an excess of amine over that required to form the neutral salts of the substituted succinic acid present.
U.S. Patent 4,502,970 relates to improved crankcase lubricating oil compositions containing lubricating oil dispersant, overbased metal detergent, zinc dialkyldithiophosphate antiwear additive and polyisobutenylsuccinic anhydride, in recited amounts. Exemplary lubricating oil formulations are disclosed containing 3 wt.% polyisobutenylsuccinimide dispersant, polyisobutenylsuccinic anhydride, overbased metal sulfonate or overbased sulfurized phenate detergents and zinc dialkyldithiophosphate antiwear agents, in base oil, in amounts of 3.0, 3.0, 2.0, 1.0 and 91.0 wt.%, respectively.
European Patent 24,146 relates to lubricating oil compositions containing copper antioxidants, and exemplifies copper antioxidants in lubricating oil compositions also containing wt.% of a 400 TBN magnesium sulphonate (containing 9.2 wt.% magnesium), 0.3 wt.% of a 250 TBN calcium phenate (containing 9.3 wt.% of calcium) and a zinc dialkyldithiophosphate in which the alkyl groups or a mixtures of such groups having between 4 and 5 carbon atoms and made by reacting phosphorous P₂S₅ with a mixture of about 65% isobutyl alcohol and 35% of amyl alcohol, to give a phosphorous level of 1.0 wt.% in lubricating oil composition.
Published British Patent Application 2,062,672 relates to additive compositions comprising sulfurized alkyl phenol and an oil soluble carboxylic dispersant containing a hydrocarbon base radical having a number average molecular weight of at least 1300, which is disclosed in combination with ash-producing detergents.
However, it is extremely difficult to translate lube oil developments intended for passenger car and light truck service, whether gasoline or light duty diesel engines, into lubricating oils intended for use in heavy duty diesel service.
R.D. Hercamp, SAE Technical Paper Series, Paper No. 831720 (1983) reports development work on engine test procedures to measure the relative ability of various lubricant formulations to control oil consumption in heavy duty diesel engines. The author indicates that lab analysis of crown land deposits on the diesel engine pistons show an organic binder to be present which contains high molecular weight esters, and the author speculates that oxidation products in the oil may be precursors for the binderfound in the deposits. It is indicated that improved antioxidants could be the key to prevent premature loss of oil consumption.
A.A. Schetelich, SAE Technical Paper Series, Paper No. 831722 (1983) reports on the effect of lubricating oil parameters on PC-1 type heavy duty diesel lubricating oil performance. It is noted that over the past 30 years, the trend in heavy duty diesel oil industry has been to decrease the sulfated ash levels from 2.5 wt.% sulfated ash (SASH) in 1960 to the typical North American SASH level of 0.8 to 1 wt.%, and to correspondingly decrease the HD oils total base number (TBN) D2896 values from over 20 to the present typical North American TBN values of from 7 to 10. Such reductions in SASH and TBN levels are attributed by the author to be due to improvement in performance of ashless components, including ashless diesel detergents and ashless dispersants. In diesel engine tests, no significant correlation was seen between the level of either piston deposits or oil consumption and the SASH or TBN levels, for about 1% to 2% SASH levels and about 8 to 17% TBN levels. In contrast, a significant correlation was seen between the level of ashless component treat and the amount of piston deposits (at the 92% confidence level) and oil consumption (at the 98% confidence level). It is noted by the authors that this correlation is drawn with respect to diesel fuels having average sulfur levels of less than about 0.5%. It is indicated that the level of buildup of ash is accelerated in the hotter engine areas. The author concludes that at the 97% confidence level there should be a correlation between oil consumption and piston deposits, especially top land deposits, which are believed to contribute to increased oil consumption due to two phenomena : (1) these deposits decrease the amount of blow-by flowing downwardly past the top land, which results in a decreased gas loading behind the top ring of the piston, which in turn leads to higher oil consumption ; and (2) increased bore polishing of the piston cylinder liner by the top land deposits which in turn contributes to higher oil consumption by migration of the oil into the firing chamber of the cylinder along the polished bore paths. Therefore, the Paper concluded that reduced ash in the oil should be sought to reduce top land deposits, and hence oil consumption.
This 1983 Schetelich paper reports formulation of 2 test oils, each containing about 1% SASH and having TBN levels of 10 and 9, respectively, wherein each formulated oil contained overbased metal detergent together with a zinc-source.
J.A. McGeehan, SAE Paper No. 831721, pp. 4.848-4.869 (1984) summarized the results of a series of heavy duty diesel engine tests to investigate the effect of top land deposits, fuel sulfur and lubricant viscosity on diesel engine oil consumption and cylinder bore polishing. These authors also indicated that excessive top land deposits cause high oil consumption and cylinder bore polishing, although they added that cylinder board polishing is also caused in high sulfurfuels by corrosion in oils of low alkalinity value. Therefore, they concluded that oil should provide sufficient alkalinity to minimize the corrosive aspect of bore polishing. The authors reported that an experimental 0.01% sulfated ash oil, which was tested in a AVL-Mack TZ675 (turbocharged) 120- hour test in combination with a 0.2% fuel sulfur, provided minimum top land deposits and very low oil consumption, which was said to be due to the "very effective ashless inhibitor". This latter component was not further defined. Further, from the data presented by the author in Figure 4 of this Paper, there do not appear to be oil consumption credits to reducing the ash level below 1 %, since the oil consumption in the engine actually rose upon reducing the SASH from 1 to 0.01 %. This reinforces the author's view that a low, but significant SASH level is required for sufficient alkalinity to avoid oil consumption as a result of bore polishing derived from corrosive aspects of the oil.
McGeehan concluded that the deposits on the top land correlate with oil consumption but are not directly related to the lubricant sulfated ash, and commented that these deposits can be controlled by the crankcase oil formulation.

SUMMARY OF THE INVENTION

In accordance with the present invention, there are provided ashless heavy duty diesel lubricating oil compositions which comprise an oil of lubricating viscosity as the major component and as the minor component (A) at least 3 wt.% of at least one ashless dispersant, (B) at least 2 wt.% of at least one sulfurized alkyl phenol, and (C) at least 0.1 wt.% of at least one organo-sulfur compound of the formula
wherein R⁴and R⁵ are straight or branched chain alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, and w and z are numbers from 1 to about 8, wherein the lubricating oil is characterized by a total sulfated ash (SASH) level of less than 0.01 wt.%.
The improved oils of the present invention are particularly useful in diesel engines powered by low sulfur fuels. Therefore, the present invention also provides a method for improving the performance of a heavy duty diesel lubricating oil adapted for use in a diesel engine provided with at least one tight top land piston, and preferably further adapted for being powered by a normally liquid fuel having a sulfur content of less than 1 wt.%, which comprises controlling the metal content of the oil to provide a total sulfated ash (SASH) level in said oil of less than 0.01 wt.%, and providing in said oil (A) at least about 3 wt.% ashless dispersant, (B) at least about 2 wt.% sulfurized alkyl phenol oxidation inhibitor, and (C) a copper corrosion inhibiting amount of at least one organo-sulfur compound of the formula
wherein R⁴ and R⁵ are straight or branched chain alkyl, cyclic, alicyclic, aryl, alkaryl or aralkyl radicals having from 2 to 30 carbon atoms, and w and z are numbers from 1 to about 8.

DETAILED DESCRIPTION OF THE INVENTION

Component A

Ashless, nitrogen or ester containing dispersants useful in this invention comprise boron-free members selected from the group consisting of (i) oil soluble salts, amides, imides, oxazolines and esters, or mixtures thereof, of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides ; (ii) long chain aliphatic hydrocarbon having a polyamine attached directly thereto ; and (iii) Mannich condensation products formed by condensing about a molar proportion of long chain hydrocarbon substituted phenol with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of polyalkylene polyamine ; wherein said long chain hydrocarbon group in (i), (ii) and (iii) is a polymer of a C₂ to C_lo, e.g., C₂ to C₅ monoolefin, said polymer having a number average molecular weight of about 300 to about 5000.
A(i) Nitrogen- or ester- containing ashless dispersants comprise members selected from the group consisting of oil soluble salts, amides, imides, oxazolines and esters, or mixtures thereof, of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides wherein said long chain hydrocarbon group is a polymer of a C₂ to C_lo, e.g., C₂ to C₅, monoolefin, said polymer having a number average molecular weight of from about 700 to 5000.
The long chain hydrocarbyl substituted mono or dicarboxylic acid material, i.e. acid, anhydride, or ester, used in the dispersant includes long chain hydrocarbon, generally a polyolefin, substituted with an average of from about 0.8 to 2.0, preferably from about 1.0 to 1.6, e.g., 1.1 to 1.3 moles, per mole of polyolefin, of an alpha or beta- unsaturated C₄ to C₁₀ dicarboxylic acid, or anhydride or ester thereof. Exemplary of such monocarboxylic acids and dicarboxylic acids, anhydrides and esters thereof are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc.
Preferred olefin polymers for reaction with the unsaturated dicarboxylic acids to form the dispersants are polymers comprising a major molar amount of C₂ to C_lo, e.g. C₂ to C₅ monoolefin. Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene, etc. The polymers can be homopolymers such as polyisobutylene, as well as copolymers of two or more of such olefins such as copolymers of : ethylene and propylene ; butylene and isobutylene ; propylene and isobutylene ; etc. Other copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 10 mole %, is a C₄ to C₁₈ non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene : or a copolymer of ethylene, propylene and 1,4 -hexadiene ; etc.
In some cases, the olefin polymer may be completely saturated, for example an ethylene-propylene copolymer made by a Ziegler-Natta synthesis using hydrogen as a moderator to control molecular weight.
The olefin polymers used in the dispersants will usually have number average molecular weights within the range of about 700 and about 5,000, more usually between about 800 and about 3000, typically from 1500 to 3000. Particularly useful olefin polymers have number average molecular weights within the range of about 900 and about 2500 with approximately one terminal double bond per polymer chain. An especially useful starting material for highly potent dispersant additives is polyisobutylene. The number average molecular weight for such polymers can be determined by several known techniques. A convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular weight distribution information, see W. W. Yau, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.
Processes for reacting the olefin polymer with the C_4-10 unsaturated dicarboxylic acid, anhydride or ester are known in the art. For example, the olefin polymer and the dicarboxylic acid material may be simply heated together as disclosed in U.S. Patents 3,361,673 and 3,401,118 to cause a thermal "ene" reaction to take place. Or, the olefin polymer can be first halogenated, for example, chlorinated or brominated to about 1 to 8 wt.%, preferably 3 to 7 wt.% chlorine, or bromine, based on the weight of polymer, by passing the chlorine or bromine through the polyolefin at a temperature of 60 to 250°C, e.g. 120 to 160°C, for about 0.5 to 10, preferably 1 to 7 hours. The halogenated polymer may then be reacted with sufficient unsaturated acid or anhydride at 100 to 250°C, usually about 180° to 235°C, for about 0.5 to 10, e.g. 3 to 8 hours, so the product obtained will contain the desired number of moles of the unsaturated acid per mole of the halogenated polymer. Processes of this general type are taught in U.S. Patents 3,087,436 ; 3,172,892 ; 3,272,746 and others.
Alternatively, the olefin polymer, and the unsaturated acid material are mixed and heated while adding chlorine to the hot material. Processes of this type are disclosed in U.S. Patents 3,215,707 ; 3,231,587 ; 3,912,764 ; 4,110,349 ; 4,234,435 ; and in GB 1,440,219.
By the use of halogen, about 65 to 95 wt.% of the polyolefin, e.g. polyisobutylene will normally react with the dicarboxylic acid material. Upon carrying out a thermal reaction without the use of halogen or a catalyst, then usually only about 50 to 75 wt.% of the polyisobutylene will react. Chlorination helps increase the reactivity. For convenience, the aforesaid functionality ratios of dicarboxylic acid producing units to polyolefin, e.g., 0.8 to 2.0, etc. are based upon the total amount of polyolefin, that is, the total of both the reacted and unreacted polyolefin, used to make the product.
The dicarboxylic acid producing materials can also be further reacted with amines, alcohols, including polyols, amino-alcohols, etc., to form other useful dispersant additives. Thus, if the acid producing material is to be further reacted, e.g., neutralized, then generally a major proportion of at least 50 percent of the acid units up to all the acid units will be reacted.
Amine compounds useful as nucleophilic reactants for neutralization of the hydrocarbyl substituted dicarboxylic acid materials include mono- and (preferably) polyamines, most preferably polyalkylene polyamines, of about 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total carbon atoms and about 1 to 12, preferably 3 to 12, most preferably 3 to 9, and typicall 5 to 7 nitrogen atoms in the molecule. A preferred class of amines are polyethylenepolyamines. These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy groups, amide groups, nitriles imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful. Preferred amines are aliphatic saturated amines, including those of the general formulas :
wherein R, R', R" and R"'are independently selected from the group consisting of hydrogen ; C₁ to C₂₅ straight or branched chain alkyl radicals ; C₁ to C₁₂ alkoxy C₂ to C₆ alkylene radicals ; C₂ to C₁₂ hydroxy amino alkylene radicals ; and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals ; and wherein R"'can additionally comprise a moiety of the formula :
wherein R' is as defined above, and wherein s and s' can be the same or a different number of from 2 to 6, preferably 2 to 4 ; and t and t' can be the same or different and are numbers of from 0 to 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t' is not greater than 15. To assure a facile reaction, it is preferred that R, R', R", R"', s, s', t and t' be selected in a manner sufficient to provide the compounds of Formulas I and II with typically at least one primary or secondary amine group, preferably at least two primary or secondary amine groups. This can be achieved by selecting at least one of said R, R', R" or R'" groups to be hydrogen or by letting t in Formula IV be at least one when R is H or when the III moiety possesses a secondary amino group. The most preferred amine of the above formulas are represented by Formula II and contain at least two primary amine groups and at least one, and preferably at least three, secondary amine groups.
Non-limiting examples of suitable amine compounds include : 1,2-diaminoethane ; 1,3-diaminopropane ; 1,4-diaminobutane ; 1,6-diaminohexane : polyethylene amines such as diethylene triamine : triethylene tet- ramine ; tetraethylene pentamine ; polypropylene amines such as 1,2-propylene diamine ; di-(1,2-propylene)triamine; di-(1,3-propylene) triamine ; N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine ; N,N-di(2-hydroxyethyl)-1,3-propylene diamine ; 3-dodecyloxypropylamine ; N-dodecyl-1,3-propane diamine ; tris hydroxy-methylaminomethane (THAM); diisopropanol amine ; diethanol amine ; triethanol amine ; mono-, di-, and tri-tallow amines ; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof.
Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines of the general formula (IV) :
wherein p₁ and _P2 are the same or different and are each integers of from 1 to 4, and n₁, n₂and n₃ are the same or different and are each integers of from 1 to 3. Non-limiting examples of such amines include 2-pentadecyl imidazoline ; N-(2-aminoethyl) piperazine ; etc.
Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylenetetramine, tetraethylene pentamine and isomeric piperazines. Low cost poly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.
Useful amines also include polyoxyalkylene polyamines such as those of the formulae :
where m has a value of about 3 to 70 and preferably 10 to 35 ; and
where "n" has a value of about 1 to 40 with the provision that the sum of all the n's is from about 3 to about 70 and preferably from about 6 to about 35, and R is a polyvalent saturated hydrocarbon radical of up to ten carbon atoms wherein the number of substituents on the R group is represented by the value of "a", which is a number of from 3 to 6. The alkylene groups in either formula (V) or (VI) may be straight or branched chains containing about 2 to 7, and preferably about 2 to 4 carbon atoms.
The polyoxyalkylene polyamines of formulas (V) or (VI) above, preferably polyoxyalkylene diamines and polyoxyalkylene triamines, may have average molecular weights ranging from about 200 to about 4000 and preferably from about 400 to about 2000. The preferred polyoxyalkylene polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2000. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under the trade name "Jef- famines D-230, D-400, D-1000, D-2000, T-403", etc.
The amine is readily reacted with the selected dicarboxylic acid material, e.g. alkenyl succinic anhydride, by heating an oil solution containing 5 to 95 wt.% of dicarboxylic acid material to about 100 to 250°C, preferably 125 to 175°C., generally for 1 to 10, e.g. 2 to hours until the desired amount of water is removed. The heating is preferably carried out to favor formation of imides or mixtures of imides and amides, rather than amides and salts. Reaction ratios of dicarboxylic material to equivalents of amine as well as the other nucleophilic reactants described herein can vary considerably, depending on the reactants and type of bonds formed. Generally from 0.1 to 1.0, preferably from about 0.2 to 0.6, e.g., 0.4 to 0.6, moles of dicarboxylic acid moiety content (e.g., grafted maleic anhydride content) is used per equivalent of nucleophilic reactant, e.g., amine. For example, about 0.8 mole of a pentaamine (having two primary amino groups and five equivalents of nitrogen per molecule) is preferably used to convert into a mixture of amides and imides, the product formed by reacting one mole of olefin with sufficient maleic anhydride to add 1.6 moles of succinic anhydride groups per mole of olefin, i.e., preferably the pentaamine is used in an amount sufficient to provide about 0.4 mole (that is, 1.6 divided by (0.8 x 5) mole) of succinic anhydride moiety per nitrogen equivalent of the amine.
The nitrogen containing dispersants can be further treated by boration as generally taught in U.S. Patent Nos. 3,087,936 and 3,254,025. This is readily accomplished by treating the selected acyl nitrogen dispersant with a boron compound selected from the class consisting of boron oxide, boron halides, boron acids and esters of boron acids in an amount to provide from about 0.1 atomic proportion of boron for each mole of said acylated nitrogen composition to about 20 atomic proportions of boron for each atomic proportion of nitrogen of said acylated nitrogen composition. Usefully the dispersants of the inventive combination contain from about 0.05 to 2.0 wt.%, e.g. 0.05 to 0.7 wt.% boron based on the total weight of said borated acyl nitrogen compound. The boron, which appears to be in the product as dehydrated boric acid polymers (primarily (HB0₂)₃), is believed to attach to the dispersant imides and diimides as amine salts, e.g., the metaborate salt of said diimide.
Treating is readily carried out by adding from about 0.05 to 4, e.g. 1 to 3 wt.% (based on the weight of said acyl nitrogen compound) of said boron compound, preferably boric acid which is most usually added as a slurry to said acyl nitrogen compound and heating with stirring at from about 135°C. to 190, e.g. 140-170°C., for from 1 to 5 hours followed by nitrogen stripping at said temperature ranges. Or, the boron treatment can be carried out by adding boric acid to the hot reaction mixture of the dicarboxylic acid material and amine while removing water.
The tris(hydroxymethyl) amino methane (THAM) can be reacted with the aforesaid acid material to form amides, imides or ester type additives as taught by GB 984,409, or to form oxazoline compounds and borated oxazoline compounds as described, for example, in U.S. 4,102,798 ; 4,116,876 and 4,113,639.
The ashless dispersants may also be esters derived from the aforesaid long chain hydrocarbon substituted dicarboxylic acid material and from hydroxy compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols, etc. The polyhydric alcohols are the most preferred hydroxy compound and preferably contain from 2 to about 10 hydroxy radicals, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and other alkylene glycols in which the alkylene radical contains from 2 to about 8 carbon atoms. Other useful polyhydric alcohols include glycerol, mono-oleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof.
The ester dispersant may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, l-cyciohexane-3-oi, and oleyl alcohol. Still other classes of the alcohols capable of yielding the esters of this invention comprise the ether-alcohols and amino-alcohols including, for example, the oxy-alkylene, oxy-arylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxy-alkylene, amino-alkylene or amino-arylene oxy-arylene radicals. They are exemplified by Cellosolve, Carbitol, N,N,N',N'-tetrahydroxy-trimethylene di-amine, and ether-alcohols having up to about 150 oxy-alkylene radicals in which the alkylene radical contains from 1 to about 8 carbon atoms.
The ester dispersant may be di-esters of succinic acids or acidic esters, i.e., partially esterified succinic acids ; as well as partially esterified polyhydric alcohols or phenols, i.e., esters having free alcohols or phenolic hydroxyl radicals. Mixtures of the above illustrated esters likewise are contemplated within the scope of this invention.
The ester dispersant may be prepared by one of several known methods as illustrated for example in U.S. Patent 3,381,022. The ester dispersants may also be borated, similar to the nitrogen containing dispersants, as described above.
Hydroxyamines which can be reacted with the aforesaid long chain hydrocarbon substituted dicarboxylic acid materials to form dispersants include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1, 3-propane-diol, 2-amino-2-ethyl-1, 3-propanediol, N-(beta-hydroxy-propyl)-N,-(beta-aminoethyl)-piperazine, tris(hydroxymethyl) amino-methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine, beta-(beta-hyd- roxyethoxy)ethylamine, and the like. Mixtures of these or similar amines can also be employed. The above description of nucleophilic reactants suitable for reaction with the hydrocarbyl substituted dicarboxylic acid or anhydride includes amines, alcohols, and compounds of mixed amine and hydroxy containing reactive functional groups, i.e., amino-alcohols.
A preferred group of ashless dispersants are those derived from polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines, e.g. tetraethylene pentamine, pentaethylene hexamine, polyoxyethylene and polyoxypropylene amines, e.g. polyoxypropylene diamine, trismethylolaminomethane and pentaerythritol, and combinations thereof. One particularly preferred dispersant combination involves a combination of (i) polyisobutene substituted with succinic anhydride groups and reacted with (ii) a hydroxy compound, e.g. pentaerythritol, (iii) a polyoxyalkylene polyamine, e.g. polyoxypropylene diamine, and (iv) a polyalkylene polyamine, e.g. polyethylene diamine and tetraethylene pentamine using about 0.3 to about 2 moles each of (ii) and (iv) and about 0.3 to about 2 moles of (iii) per mole of (i) as described in U.S. Patent 3,804,763. Another preferred dispersant combination involves the combination of (i) polyisobutenyl succinic anhydride with (ii) a polyalkylene polyamine, e.g. tetraethylene pentamine, and (iii) a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine, e.g. pentaerythritol or trismethylolaminomethane as described in U.S. Patent 3,632,511.
A(ii) Also useful as ashless nitrogen-containing dispersant in this invention are dispersants wherein a nitrogen containing polyamine is attached directly to the long chain aliphatic hydrocarbon as shown in U.S. Patents 3,275,554 and 3,565,804 where the halogen group on the halogenated hydrocarbon is displaced with various alkylene polyamines.
A(iii) Another class of nitrogen containing dispersants which may be used are those containing Mannich base or Mannich condensation products as they are known in the art. Such Mannich condensation products generally are prepared by condensing about 1 mole of a high molecularweight hydrocarbyl substituted mono-or polyhydroxy benzene (e.g., having a number average molecular weight of 1,000 or greater) with about 1 to 2.5 moles of formaldehyde or paraformaldehyde and about 0.5 to 2 moles polyalkylene polyamine as disclosed, e.g., in U.S. Patents 3,442,808 ; 3,649,229 and 3,798,165 (the disclosures of which are hereby incorporated by reference in their entirety). Such Mannich condensation products may include a long chain, high molecular weight hydrocarbon on the phenol group or may be reacted with a compound containing such a hydrocarbon, e.g., polyalkenyl succinic anhydride as shown in said aforementioned U.S. Patent 3,442,808.

Component B

Component B of the compositions of this invention is at least one sulfurized alkyl phenol as oxidation inhibitor. Sulfurized alkyl phenols and the methods of preparing them are known in the art and are disclosed, for example, in the following U.S. Patents (which are incorporated by reference herein) : 2,139,766 ; 2,198,828 ; 2,230,542 ; 2,836,565 ; 3,285,854 ; 3,538,166 ; 3,844,956 ; and 3,951,830.
In general, the sulfurized alkyl phenol may be prepared by reacting an alkyl phenol with a sulfurizing agent such as elemental sulfur, a sulfur halide (e.g., sulfur monochloride or sulfur dichloride), a mixure of hydrogen sulfide and sulfur dioxide, or the like. The preferred sulfurizing agents are sulfur and the sulfur halides, and especially the sulfur chlorides, with sulfur dichloride (SC1₂) being especially preferred.
The alkyl phenols which are sulfurized to produce component B are generally compounds containing at least one hydroxy group and at least one alkyl radical attched to the same aromatic ring. The alkyl radical ordinarily contains about 3-100 and preferably about 6-20 carbon atoms. The alkyl phenol may contain more than one hydroxy group as exemplified by alkyl resorcinols, hydroquinones and catechols, or it may contain more than one alkyl radical ; but normally it contains only one of each. Compounds in which the alkyl and hydroxy groups are ortho, meta and para to each other, and mixtures of such compounds, are within the scope of the invention. Illustrative alkyl phenols are n-propylphenol, isopropyl phenol, n-butylphenol, t-butylphenol, hexyl- phenol, heptylphenol, octylphenol, nonylphenol, n-dodecylphenol, (propene tetramer) -substituted phenol, octadecylphenol, elcosylphenol, polybutene (molecular weight about 1000) -substituted phenol, n-dodecyl- resorcinol and 2,4-di-t-butylphenol. Also included are methylene-bridged alkyl phenols of the type which may be prepared by the reaction of an alkyl phenol with formaldehyde or a formaldehyde-yielding reagent such as trioxane or paraformaldehyde.
The sulfurized alkyl phenol is typically prepared by reacting the alkyl phenol with the sulfurizing agent at a temperature within the range of about 100-250°C. The reaction may take place in a substantially inert diluent such as toluene, xylene, petroleum naphtha, mineral oil, Cellosolve or the like. If the sulfurizing agent is a sulfur halide, and especially if no diluent is used, it is frequently preferred to remove acidic materials such as hydrogen halides by vacuum stripping the reaction mixture or blowing it with an inert gas such as nitrogen. If the sulfurizing agent is sulfur, it is frequently advantageous to blow the sulfurized product with an inert gas such as nitrogen or air so as to remove sulfur oxides and the like.

Component C

Component C of the present invention is a copper corrosion inhibitor and comprises at least one hydrocarbon polysulfide derivative of 2,5-dimercapto-1,3,4-thiadiazole having the formula :
wherein R⁴and R⁵ are straight or branched chain alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, and w and z are numbers from 1 to about 8. Preferably R⁴ and R⁵ each have from 4 to about 16 carbon atoms, and most preferably from about 8 to about 14 carbon atoms, and preferably the values of "w" and "z" are numbers of from 1 to 4.
The herein-described polysulfide derivatives of 2, 5-dimercapto-1, 3, 4-thiadiazole can be suitably prepared by several methods. For example, they can be prepared by reacting 2, 5-dimercapto-1, 3, 4-thiadiazole with a suitable sulfenyl chloride, or by reacting the dimercaptan with chlorine and reacting the resultant disulfenyl chloride below
with a primary or tertiary mercaptan. Bis-trisulfide derivatives are obtained by reacting the dimercaptan with a mercaptan and a sulfur chloride in molar ratios of from 1 : 2 : 2 to 1 : 2 : 4 at a temperature of from 49 to 100°C (120° to 212°F). Higher polysulfides may be prepared by reacting the thiadiazole di- or trisulfides with sulfur at temperatures of 93 to 204°C (200°F to 400°F). Another method of preparing the polysulfides of the present invention involves reacting 2,5-dimercapto-1,3,4-thiadiazole with a mercaptan and sulfur in the molar ratio of from 1 : 1 : 1 to 1 : 4 : 16 at temperatures of from 71 to 179°C (160°F to 300°F).
Compounds produced in accordance with the above procedure preferably are polysulfides of 1,3,4-thiadiazole-2,5-bis(alkyl, di-tri or tetra sulfide) containing from 2 to about 30 carbon atoms. Desirable polysulfides include 1, 3, 4-thiadiazole-2, 5-bis (octyldisulfide) ; 1,3,4-thiadiazole-2,5-bis(octyltrisulfide) ; 1,3,4-thiadiazole-2,5-bis (octyltetrasulfide) ; 1 ,3,4-thiadiazole-2,5-(nonyldisulfide) ; 1,3,4-thiadiazole 2,5-(nonyltrisulfide) ; 1,3,4-thiadiazole-2,5-(nonyltetrasulfide) ; 1 ,3,4-thiadiazole-2,5-bis(dodecyldisulfide) ; 1 ,3,4-thiadiazole-2,5-bis(dodecyltrisulfide) ; 1,3,4-thiadiazole-2,5-bis(dodecyltetrasulfide 2-lauryldithia-5-thiaalphamethylstyryl-1,3,4-thiadiazole and 2-lauryltrithia-5-thiaalphamethylstyryl-1,3,4-thiadiazole and mixtures thereof. Preferred materials are the derivatives of 1,3,4-thiadiazoles such as those described in U.S. Patents 2,719,125 ; 2,719,126 ; and 3,087,932 ; especially preferred is the compound 2,5-bis (t-octadithio)-1,3,4 thiadiazole commercially available as Amoco 150, and 2,5-bis(nonyldithio)-1,3,4-thiadiazole, commercially available as Amoco 158.
Preparation of Component C is further described in U.S. Patents 2,719,125 ; 2,719,126 ; 3,087,932 ; and 4,410,436.

LUBRICATING COMPOSITIONS

Lubricating oil compositions, e.g. automatic transmission fluids, heavy duty oils suitable for diesel engines (that is, compression ignition engines), etc., can be prepared with the additives of the invention. Universal type crankcase oils wherein the same lubricating oil compositions can be used for both gasoline and diesel engine can also be prepared. These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are required in the formulations. Among these types of additives are included viscosity index improvers, ashless antioxidants, ashless corrosion inhibitors, pour point depressants, ashless antiwear agents, etc., provided the fully formulated oil satisfies the ashless SASH requirements of this invention.
In the preparation of heavy duty diesel lubricating oil formulations it is common practice to introduce the additives in the form of 10 to 80 wt.%, e.g. 20 to 80 wt.% active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent. Usually these concentrates may be diluted with 3 to 100, e.g. 5 to 40 parts by weight of lubricating oil, per part by weight of the additive package, in forming finished lubricants, e.g. crankcase motor oils. The purpose of concentrates, of course, is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend. Thus, a Component A ashless dispersant would be usually employed in the form of a 40 to 50 wt.% concentrate, for example, in a lubricating oil fraction.
Components A, B and C of the present invention will be generally used in admixture with a lube oil basestock, comprising an oil of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
Components A, B and C can be incorporated into a lubricating oil in any convenient way. Thus, these mixtures can be added directly to the oil by dispersing or dissolving the same in the oil at the desired level of concentrations of the detergent inhibitor and antiwear agent, respectively. Such blending into the additional lube oil can occur at room temperature or elevated temperatures. Alternatively, the Components A, B and C can be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and then blending the concentrate with a lubricating oil basestock to obtain the final formulation. Such concentrates will typically contain (on an active ingredient (A.I.) basis) from about 10 to about 70 wt.%, and preferably from about 30 to about 60 wt.%, Component A ashless dispersant additives, typically from about 10 to 40 wt.%, preferably from about 10 to 30 wt.% Component B antioxidant additive, typically from about 0.5 to 5 wt.%, and preferably from about 0.6 to 3 wt.%, component C copper corrosion inhibitor, and typically from about 30 to 80 wt.%, preferably from about 40 to 60 wt.%, base oil, based on the concentrate weight.
The compositions of this invention are also characterized as being ashless, that is, by a total sulfate ash value (SASH) concentration of less than 0.01 wt.% SASH, preferably substantially zero. By "total sulfated ash" herein is meant the total weight % of ash which is determined for a given oil (based on the oil's metallic components) by ASTM D874.
The lubricating oil basestock for Components A, B and C typically is adapted to perform a selected function by the incorporation of additional additives therein to form lubricating oil compositions (i.e., formulations).
Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid petroleum oils and hyd- rorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-poly isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500) ; and mono-and polycarboxylic esters thereof, for example, the acetic acid esters mixed C₃-C₈ fatty acid esters and C₁₃ Oxo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
Esters useful as synthetic oils also include those made from C₅ to C₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants ; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tertbutylphenyl) silicate, hexa-(4-methyl-2-pentoxy) disiloxane, poly(methyl) siloxanes and poly(methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
Unrefined, refined and rerefined oils can be used in the lubricants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
The novel compositions of the present invention can be used with V.I improvers to form multi-grade diesel engine lubricating oils. Viscosity modifiers impart high and low temperature operability to the lubricating oil and permit it to remain relatively viscous at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures. Viscosity modifiers are generally high molecular weight hydrocarbon polymers including polyesters. The viscosity modifiers may also be derivatized to include other properties or functions, such as the addition of dispersancy properties. These oil soluble viscosity modifying polymers will generally have number average molecular weights of from 10³ to 10⁶, preferably 10⁴ to 10⁶, e.g., 20,000 to 250,000, as determined by gel permeation chromatography or osmometry.
Examples of suitable hydrocarbon polymers include homopolymers and copolymers of two or more monomers of C₂ to C₃₀, e.g. C₂ to C₈ olefins, including both alpha olefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc. Frequently they will be of ethylene with C₃ to C₃₀ olefins, particularly preferred being the copolymers of ethylene and propylene. Other polymers can be used such as polyisobutylenes, homopolymers and copolymers of C₆ and higher alpha olefins, atactic polypropylene, hydrogenated polymers and copolymers and terpolymers of styrene, e.g. with isoprene and/or butadiene and hydrogenated derivatives thereof. The polymer may be degraded in molecular weight, for example by mastication, extrusion, oxidation or thermal degradation, and it may be oxidized and contain oxygen. Also included are derivatized polymers such as post-grafted interpolymers of ethylene-propylene with an active monomer such as maleic anhydride which may be further reacted with an alcohol, or amine, e.g. an alkylene polyamine or hydroxy amine, e.g. see U.S. Patent Nos. 4,089,794; 4,160,739; 4,137,185; or copolymers of ethylene and propylene reacted or grafted with nitrogen compounds such as shown in U.S. Patent Nos. 4,068,056 ; 4,068,058 ; 4,146,489 and 4,149,984.
The preferred hydrocarbon polymers are ethylene copolymers containing from 15 to 90 wt.% ethylene, preferably 30 to 80 wt.% of ethylene and 10 to 85 wt.%, preferably 20 to 70 wt.% of one or more C₃ to C₂₈, preferably C₃ to C₁₈, more preferably C₃ to C₈, alpha-olefins. While not essential, such copolymers preferably have a degree of crystallinity of less than 25 wt.%, as determined by X-ray and differential scanning calorimetry. Copolymers of ethylene and propylene are most preferred. Other alpha-olefins suitable in place of propylene to form the copolymer, or to be used in combination with ethylene and propylene, to form a terpolymer, tetrapolymer, etc., include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. also branched chain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene-1 , 4,4- dimethyl-1-pentene, and 6-methylheptene-1, etc., and mixtures thereof.
Terpolymers, tetrapolymers, etc., of ethylene, said C₃-C₂₈ alpha-olefin, and a non-conjugated diolefin or mixtures of such diolefins may also be used. The amount of the non-conjugated diolefin generally ranges from about 0.5 to 20 mole percent, preferably from about 1 to about 7 mole percent, based on the total amount of ethylene and alpha-olefin present.
The polyester V.I. improvers are generally polymers of esters of ethylenically unsaturated C₃ to C₈ mono-and dicarboxylic acids such as methacrylic and acrylic acids, maleic acid, maleic anhydride, fumaric acid, etc.
Examples of unsaturated esters that may be used include those of aliphatic saturated mono alcohols of at least 1 carbon atom and preferably of from 12 to 20 carbon atoms, such as decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and the like and mixtures thereof.
Other esters include the vinyl alcohol esters of C₂ to C₂₂ fatty or mono carboxylic acids, preferably saturated such as vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and the like and mixtures thereof. Copolymers of vinyl alcohol esters with unsaturated acid esters such as the copolymer of vinyl acetate with dialkyl fumarates, can also be used.
The esters may be copolymerized with still other unsaturated monomers such as olefins, e.g. 0.2 to 5 moles of C₂-C₂₀ aliphatic or aromatic olefin per mole of unsaturated ester, or per mole of unsaturated acid or anhydride followed by esterification For example, copolymers of styrene with maleic anhydride esterified with alcohols and amines are known, e.g., see U.S. Patent 3,702,300.
Such ester polymers may be grafted with, or the ester copolymerized with, polymerizable unsaturated nitrogen-containing monomers to impart dispersancy to the V.I. improvers. Examples of suitable unsaturated nitrogen-containing monomers include those containing 4 to 20 carbon atoms such as amino substituted olefins as p-(beta-diethylaminoethyl)styrene ; basic nitrogen-containing heterocycles carrying a polymerizable ethylenically unsaturated substituent, e.g. the vinyl pyridines and the vinyl alkyl pyridines such as 2-vinyl-5-ethyl pyridine, 2-methyl-5-vinyl pyridine, 2-vinyl-pyridine, 4-vinyl-pyridine, 3-vinyl-pyridine, 3-methyl-5-vinyl-pyridine, 4-methyl-2-vinyl-pyridine, 4-ethyl-2-vinyl-pyridine and 2-butyl-1-5-vinyl-pyridine and the like.
N-vinyl lactams are also suitable, e.g. N-vinyl pyrrolidones or N-vinyl piperidones.
The vinyl pyrrolidones are preferred and are exemplified by N-vinyl pyrrolidone, N-(1-methylvinyl) pyrrolidone, N-vinyl-5-methyl pyrrolidone, N-vinyl-3, 3-dimethylpyrrolidone, N-vinyl-5-ethyl pyrrolidone, etc.
Other antioxidants useful in this invention include oil soluble copper compounds. The copper may be blended into the oil as any suitable oil soluble copper compound. By oil soluble we mean the compound is oil soluble under normal blending conditions in the oil or additive package. The copper compound may be in the cuprous or cupric form. The copper may be in the form of the copper dihydrocarbyl thio- or dithio-phosphates wherein copper may be substituted for zinc in the compounds and reactions described above although one mole of cuprous or cupric oxide may be reacted with one or two moles of the dithiophosphoric acid, respectively. Alternatively the copper may be added as the copper salt of a synthetic or natural carboxylic acid. Examples include C₁₀ to C₁₈ fatty acids such as stearic or palmitic, but unsaturated acids such as oleic or branched carboxylic acids such as naphthenic acids of molecular weight from 200 to 500 or synthetic carboxylic acids are preferred because of the improved handling and solubility properties of the resulting copper carboxylates Also useful are oil soluble copper dithio carbamates of the general formula (RR'NCSS)_nCu, where n is 1 or 2 and R and R' are the same or different hydrocarbyl radicals containing from 1 to 18 and preferably 2 to 12 carbon atoms and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc. In order to obtain oil solubility, the total number of carbon atoms (i.e, Rand R') will generally be about 5 or greater. Copper sulphonates, phenates, and acetylacetonates may also be used.
Exemplary of useful copper compounds are copper (Cu^l and/or Cu") salts of alkenyl succinic acids or anhydrides. The salts themselves may be basic, neutral or acidic. They may be formed by reacting (a) any of the materials discussed above in the Ashless Dispersant section, which have at least one free carboxylic acid (or anhydride) group with (b) a reactive metal compound. Suitable acid (or anhydride) reactive metal compounds include those such as cupric or cuprous hydroxides, oxides, acetates, borates, and carbonates or basic copper carbonate.
Examples of the metal salts of this invention are Cu salts of polyisobutenyl succinic anhydride (hereinafter referred to as Cu-PIBSA), and Cu salts of polyisobutenyl succinic acid. Preferably, the selected metal employed is its divalent form, e.g., CU+2. The preferred substrates are polyalkenyl succinic acids in which the alkenyl group has a number average molecular weight (M_n) greater than about 700. The alkenyl group desirably has a M_n from about 900 to 1400, and up to 2500, with a M_n of about 950 being most preferred. Especially preferred, of those listed above in the section on Dispersants, is polyisobutylene succinic acid (PIBSA). These materials may desirably be dissolved in a solvent, such as a mineral oil, and heated in the presence of a water solution (or slurry) of the metal bearing material. Heating may take place between 70 and about 200°C. Temperatures of 110° to 140°C are entirely adequate. It may be necessary, depending upon the salt produced, not to allow the reaction to remain at a temperature above about 140°C for an extended period of time, e.g., longer than 5 hours, or decomposition of the salt may occur.
The copper antioxidants (e.g., Cu-PIBSA, Cu-oleate, or mixtures thereof) will be generally employed in an amount of from about 50-500 ppm by weight of the metal, in the final lubricating or fuel composition.
The copper antioxidants used in this invention are inexpensive and are effective at low concentrations and therefore do not add substantially to the cost of the product. The results obtained are frequently better than those obtained with previously used antioxidants, which are expensive and used in higher concentrations. In the amounts employed, the copper compounds do not interfere with the performance of other components of the lubricating composition.
While any effective amount of the copper antioxidant can be incorporated into the lubricating oil composition, it is contemplated that such effective amounts be sufficient to provide said lube oil composition with an amount of the copper antioxidant of from about 5 to 500 (more preferably 10 to 200, still more preferably 10 to 180, and most preferably 20 to 130 (e.g., 90 to 120)) part per million of added copper based on the weight of the lubricating oil composition. Of course, the preferred amount may depend amongst other factors on the quality of the basestock lubricating oil.
Corrosion inhibitors, also known as anti-corrosive agents, reduce the degradation of the non-ferrous metallic parts contacted by the lubricating oil composition. Illustrative of corrosion inhibitors are phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol thioester, and also preferably in the presence of carbon dioxide. Phosphosulfurized hydrocarbons are prepared by reacting a suitable hydrocarbon such as a terpene, a heavy petroleum fraction of a C₂ to C₆ olefin polymer such as polyisobutylene, with from 5 to 30 weight percent of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature in the range of 65° to 320°C. Neutralization of the phosphosulfurized hydrocarbon may be effected in the manner taught in U.S. Patent No. 1,969,324.
Other oxidation inhibitors can also be employed in addition to Component B, to assist, where desired, in further reducing the tendency of the mineral oils to deteriorate in service and to thereby reduce the formation of products of oxidation such as sludge and varnish-like deposits on the metal surfaces and to reduce viscosity growth. Such other oxidation inhibitors include alkaline earth metal salts of alkylphenolthioesters having preferably C₅ to C₁₂ alkyl side chains(such as calcium nonylphenol sulfide, barium t-octylphenyl sulfide, etc.), diphenyl amine, alkyl diphenyl amines, dioctylphenylamine, phenyl alpha-naphthylamine (and its alkylated derivatives), phosphosulfurized hydrocarbons, other sulfurized hydrocarbons (such as sulfurized phenols, sulfurized alkyl catechols, and the like), phenols, hindered-phenols, bis-phenols, catechol, alkylated catechols, etc.
Friction modifiers serve to impart the proper friction characteristics to lubricating oil compositions such as automatic transmission fluids.
Representative examples of suitable friction modifiers are found in U.S. Patent No. 3,933,659 which discloses fatty acid esters and amides ; U.S. Patent No. 4,176,074 which describes molybdenum complexes of polyisobutenyl succinic anhydride-amino alkanols ; U.S. Patent No. 4,105,571 which discloses glycerol esters of dimerized fatty acids ; U.S. Patent No. 3,779,928 which discloses alkane phosphonic acid salts ; U.S. Patent No. 3,778,375 which discloses reaction products of a phosphonate with an oleamide ; U.S. Patent No. 3,852,205 which discloses S-carboxy-alkylene hydrocarbyl succinimide, S-carboxy-alkylene hydrocarbyl suc- cinamic acid and mixtures thereof ; U.S. Patent No. 3,879,306 which discloses N-(hydroxy alkyl) alkenyl-suc- cinamic acids or succinimides ; U.S. Patent No. 3,932,290 which discloses reaction products of di-(lower alkyl) phosphites and epoxides ; and U.S. Patent No. 4,028,258 which discloses the alkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl) alkenyl succinimides. The disclosures of the above references are herein incorporated by reference. The most preferred friction modifiers are glycerol mono and dioleates, and succinate esters, or metal salts thereof, of hydrocarbyl substituted succinic acids or anhydrides and thiobis alkanols such as described in U.S. Patent No. 4,344,853.
Pour point depressants lower the temperature at which the fluid will flow or can be poured. Such depressants are well known. Typical of those additives which usefully optimize the low temperature fluidity of the fluid are C₈-C_l8 dialkylfumarate vinyl acetate copolymers, polymethacrylates, and wax naphthalene.
Foam control can be provided by an antifoamant of the polysiloxane type, e.g. silicone oil and polydimethyl siloxane.
Organic, oil-soluble compounds useful as rust inhibitors in this invention comprise nonionic surfactants such as polyoxyalkylene polyols and esters thereof, and anionic surfactants such as salts of alkyl sulfonic acids. Such anti-rust compounds are known and can be made by conventional means. Nonionic surfactants, useful as anti-rust additives in the oleaginous compositions of this invention, usually owe their surfactant properties to a number of weak stabilizing groups such as ether linkages. Nonionic anti-rust agents containing ether linkages can be made by alkoxylating organic substrates containing active hydrogens with an excess of the lower alkylene oxides (such as ethylene and propylene oxides) until the desired number of alkoxy groups have been placed in the molecule.
The preferred rust inhibitors are polyoxyalkylene polyols and derivatives thereof. This class of materials are commercially available from various sources : Pluronic Polyols from Wyandotte Chemicals Corporation ; Polyglycol 112-2, a liquid triol derived from ethylene oxide and propylene oxide available from Dow Chemical Co. ; and Tergitol, dodecylphenyl or monophenyl polyethylene glycol ethers, and Ucon, polyalkylene glycols and derivatives, both available from Union Carbide Corp. These are but a few of the commercial products suitable as rust inhibitors in the improved composition of the present invention.
In addition to the polyols per se the esters thereof obtained by reacting the polyols with various carboylic acids are also suitable. Acids useful in preparing these esters are lauric acid, stearic acid, succinic acid, and alkyl- or alkenyl-substituted succinic acids wherein the alkyl-or alkenyl group contains up to about twenty carbon atoms.
The preferred polyols are prepared as block polymers. Thus, a hydroxy-substituted compound, R-(OH)n (wherein n is 1 to 6, and R is the residue of a mono- or polyhydric alcohol, phenol, naphthol, etc.) is reacted with propylene oxide to form a hydrophobic base. This base is then reacted with ethylene oxide to provide a hydrophilic portion resulting in a molecule having both hydrophobic and hydrophilic portions. The relative sizes of these portions can be adjusted by regulating the ratio of reactants, time of reaction, etc., as is obvious to those skilled in the art. Thus it is within the skill of the art to prepare polyols whose molecules are characterized by hydrophobic and hydrophilic moieties which are present in a ratio rendering rust inhibitors suitable for use in any lubricant composition regardless of differences in the base oils and the presence of other additives.
If more oil-solubility is needed in a given lubricating composition, the hydrophobic portion can be increased and/or the hydrophilic portion decreased. If greater oil-in-water emulsion breaking ability is required, the hydrophilic and/or hydrophobic portions can be adjusted to accomplish this.
Compounds illustrative of R-(OH)_n include alkylene polyols such as the alkylene glycols, alkylene triols, alkylene tetrols, etc., such as ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, and the like. Aromatic hydroxy compounds such as alkylated mono- and polyhydric phenols and naphthols can also be used, e.g., heptylphenol, dodecylphenol, etc.
Other suitable demulsifiers include the esters disclosed in U.S. Patents 3,098,827 and 2,674,619.
The liquid polyols available from Wyandotte Chemical Co. under the name Pluronic Polyols and other similar polyols are particularly well suited as rust inhibitors. These Pluronic Polyols correspond to the formula :
wherein x, y, and z are integers greater than 1 such that the -CH₂CH₂0- groups comprise from about 10% to about 40% by weight of the total molecular weight of the glycol, the average molecule weight of said glycol being from about 1000 to about 5000. These products are prepared by first condensing propylene oxide with propylene glycol to produce the hydrophobic base
This condensation product is then treated with ethylene oxide to add hydrophilic portions to both ends of the molecule. For best results, the ethylene oxide units should comprise from about 10 to about 40% by weight of the molecule. Those products wherein the molecular weight of the polyol is from about 2500 to 4500 and the ethylene oxide units comprise from about 10% to about 15% by weight of the molecule are particularly suitable. The polyols having a molecular weight of about 4000 with about 10% attributable to (CH₂CH₂0) units are particularly good. Also useful are alkoxylated fatty amines, amides, alcohols and the like, including such alkoxylated fatty acid derivatives treated with Cg to C₁₆ alkyl-substituted phenols (such as the mono- and di-heptyl, octyl, nonyl, decyl, undecyl, dodecyl and tridecyl phenols), as described in U.S. Patent 3,849,501, which is also hereby incorporated by reference in its entirety.
These compositions of our invention may also contain other additives such as those previously described, and other metal containing additives, for example, those containing barium and sodium.
Other suitable additives are the thio and polythio sulphenamides of thiadiazoles such as those described in GB Patent Specification 1,560,830. When these compounds are included in the lubricating composition, we prefer that they be present in an amount from 0.01 to 10, preferably 0.1 to 5.0 weight percent based on the weight of the composition.
Some of these numerous additives can provide a multiplicity of effects, e.g., a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein.
Compositions when containing these conventional additives are typically blended into the base oil in amounts effective to provide their normal attendant function. Representative effective amounts of such additives (as the respective active ingredients) in the fully formulated oil are illustrated as follows :
When other additives are employed, it may be desirable, although not necessary, to prepare additive concentrates comprising concentrated solutions or dispersions of the novel detergent inhibitor/antiwear agent mixtures of this invention (in concentrate amounts hereinabove described), together with one or more of said other additives (said concentrate when constituting an additive mixture being referred to herein as an additive-package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The concentrate or additive-package will typically be formulated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant. Thus, the detergent inhibitor/antiwear agent mixtures of the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive-packages containing active ingredients in collective amounts of typically from about 2.5 to about 90%, and preferably from about 15 to about 75%, and most preferably from about 25 to about 60% by weight additives in the appropriate proportions with the remainder being base oil.
The final formulations may employ typically about 10 wt.% of the additive-package with the remainder being base oil.
All of said weight percents expressed herein (unless otherwise indicated) are based on active ingredient (AI.) content of the additive, and/or upon the total weight of any additive-package, or formulation which will be the sum of the A.I. weight of each additive plus the weight of total oil or diluent.
This invention will be further understood by reference to the following examples, wherein all parts are parts by weight, unless otherwise noted and which include preferred embodiments of the invention.

EXAMPLES

A series of fully formulated SAE 15W40 lubricating oils are prepared having the components identified in Table I.
The formulations are subjected to a Cummins NTC-400 field test (loads = refrigerated trailers 36,364 kg (80,000 lbs.) gross vehicle weight), approx. 80% load factor ; continental United States service (ex-Alaska), with majority of hauling from Dallas to Pacific Northwest, wherein diesel fuels < 0,3 wt% sulfur were employed.
Also included in the above tests are the following commercial SAE 15W40 lubricating oils. These formulations include ashless dispersant, overbased alkaline earth metal detergent inhibitors and zinc dihydrocarbyl dithiophosphate antiwear agents.
The data thereby obtained are set forth in Table III.
From the data in Table III, it can be seen that the oil of Example 1 provides superior crownland cleanliness without sacrificing any of the remaining performance properites.
The ashless oils of this invention are particularly useful in heavy duty diesel engines employing roller cam followers. The ashless oils of this invention are preferably employed in heavy duty diesel engines which employ normally liquid fuels having a sulfur content of less than 1 wt.%, more preferably less than 0.5 wt.%, still more preferably less than 0.3 wt.% (e.g., from about 0.1 to about 0.3 wt.%), and most preferably less than 0.1 wt.% (e.g., from 100 to 500 ppm sulfur). Such normally liquid fuels include hydrocarbonaceous petroleum distillate fuels such as diesel fuels or fuel oils as defined by ASTM Specification D396. Compression ignited engines can also employ normally liquid fuel compositions comprising non-hydrocarbonaceous materials such as alcohols, ethers, organonitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) are also within the scope of this invention as are liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale and coal. Normally liquid fuels which are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarbonaceous materials are also contemplated. Examples of such mixtures are combinations of diesel fuel and ether. Particularly preferred is No. 2 diesel fuel.
The lubricating oils of this invention are particularly useful in the crankcase of diesel engines having cylinders (generally from 1 to 8 cylinders or more per engine) wherein there is housed for vertical cyclic reciprocation therein a piston provided with a tight top land, that is, cylinders wherein the distance between the piston's top land and the cylinder wall liner is reduced to minimize the amount of particulates generated in the cylinder's firing chamber (wherein the fuel is combusted to generate power). Such tight top lands can also provide improved fuel economy and an increase in the effective compression ratio in the cylinder. The top land comprises the region of the generally cylindrical piston above the top piston ring groove, and the top land, therefore, is generally characterized by a circular cross-section (taken along the longitudinal axis of the piston). The outer periphery of the top land can comprise a substantially vertical surface which is designed to be substantially parallel to the vertical walls of the cylinder liner. (Such top lands are herein referred to as "cylindrical top lands".) Or, as is preferred, the top land can be tapered inwardly toward the center of the piston from the point at which the top land adjoins the top piston ring groove and the uppermost surface of the piston, i.e., the "crown". The distance between the top land and the cylinder wall liner, herein called the "top land clearance", will preferably range from 0.025 to 0.026 cm (0.010 to 0.030 inch) for cylindrical top lands. For tapered top lands, the lower top land clearance (that is, the top land clearance at the point at which the top land is adjoined to the top piston ring groove) is preferably from 0.013 to 0.076 cm (0.005 to 0.030 inch), and more preferably from 0.025 to 0.051 cm (0.010 to 0.020 inch), and the upper top land clearance, that is, the top land clearance at the piston crown, is preferably from 0.025 to 0.114 cm (0.010 to 0.045 inch), and more preferably from 0.038 to 0.076 cm (0.015 to 0.030 inch). While the top land clearance can be less than the dimensions given above (e.g., less than 0.0013 cm (0.005 inch)), if such lesser distances do not result in undesired contact of the top land portion of the piston with the cylinder wall liner during operation of the engine, which is undesirable due to the resultant damage to the liner. Generally, the height of the top land (that is, the vertical distance, as measured along the cylinder wall liner, from the bottom of the top land to the top of the top land) is from 0.25 to 3.0 cm (0.1 to 1.2 inch), which is generally from 2.0 to 3.0 cm (0.8 to 1.2 inch) for 4-cycle diesel engines and from 0.25 to 1.27 cm (0.1 to 0.5 inch) for 2-cycle diesel engines. The design of diesel engines and such pistons having such tight top lands is within the skill of the skilled artisan and need not be further described herein.

Claims

1. An ashless heavy duty diesel engine lubricating oil composition which comprises a major amount of an oil of lubricating viscosity and (A) at least 3 weight percent of at least one ashless dispersant, (B) at least 2 weight percent of at least one sulfurized alkyl phenol, and (C) at least 0.1 weight percent of at least one organo-sulfur compound of the formula

wherein R⁴and R⁵ are straight or branched chain alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkyl radicals having from 2 to 30 carbon atoms, and w and z are numbers from 1 to 8, wherein the lubricating oil is characterized by a total sullated ash (SASH) level of less than 0.01 weight percent.

2. The composition of claim 1 wherein said ashless dispersant comprises at least one member selected from the group consisting of oil soluble salts, amides, imides, oxazolines and esters, and mixtures thereof, of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides wherein said long chain hydrocarbon group is a polymer of a C₂ to C₁₀ monoolefin, said polymer having a number average molecular weight of from 700 to 5000.

3. The composition of claim 2 wherein said long chain hydrocarbyl substituted mono or dicarboxylic acid material comprises a polyolefin, substituted with an average of from 0.8 to 2.0 moles, per mole of polyolefin, of a substituent group comprising an alpha or beta-unsaturated C₄ to C₁₀ monounsaturated dicarboxylic acid producing material.

4. The composition of claim 3 wherein said alpha or beta- unsaturated C₄ to C₁₀ monounsaturated dicarboxylic acid producing material comprises a dicarboxylic acid, or anhydride or ester thereof.

5. The composition of claim 4 wherein said substituent group comprises a member selected from the group consisting of fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate and chloromaleic anhydride.

6. The composition of claim 2 wherein said long chain hydrocarbyl substituted acid material comprises a polyolefin and substitutent group selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

7. The composition of claim 1 wherein said ashless dispersant comprises polyisobutenyl succinimide of a polyalkylene polyamine having an average of from 2 to 60 carbon atoms and from 1 to 12 nitrogen atoms per molecule of said polyamine, wherein said polyisobutylene moiety is derived from polyisobutylene having a number average molecular weight of from 800 to 3000.

8. The composition of any of claims 1 to 7, wherein said SASH level is zero.

9. The composition of claim 1 wherein said ashless dispersant comprises the product of (a) a hydrocarbyl substituted C₄ to C₁₀ monounsaturated dicarboxylic acid producing material formed by reacting an olefin polymer of C₂ to C₁₀ monoolefin having a number average molecular weight of weight of 700 to 5000 and a C₄ to C₁₀ monounsaturated acid material, said acid producing material having an average of 0.8 to 2.0 dicarboxylic acid producing moieties, per molecule of said olefin polymer present in the reaction mixture used to form said first acid producing material, and (b) a nucleophilic reactant selected from the group consisting of amines, alcohols, amino-alcohols and mixtures thereof.

10. The composition of claim 9 wherein said nucleophilic reactant comprises an amine.

11. The composition of claim 10 wherein said amine comprises amines containing from 2 to 60 carbon atoms and from 1 to 12 nitrogen atoms per molecule.

12. The composition of claim 11 wherein said amine comprises a polyalkylenepolyamine wherein said alkylene groups contain 2 to 40 carbons and said polyalkylenepolyamine contains from 3 to 9 nitrogen atoms per molecule.

13. The composition of claim 12 wherein said amine comprises polyethylenepolyamine.

14. The composition of claim 10 wherein said amine contains from 3 to 9 nitrogen atoms per molecule, and wherein said hydrocarbyl substituted acid producing material contains succinic moieties wherein from 0.1 to 1.0 mole of said succinic moieties containd in said olefin polymer is reacted per equivalent of said amine.

15. The composition of claim 16 wherein said ashless dispersant is borated and wherein said reaction mixture includes boric acid.

16. The composition of claim 15 wherein said reaction product contains 0.05 to 2.0 weight percent boron.

17. The composition of any of claims 9 to 16 wherein said number average molecular weight of said olefin polymer is from 1500 to 3000, and wherein said amine comprises a polyalkylene polyamine having an average of from 5 to 7 nitrogen atoms per molecule.

18. The composition of any of claims 9 to 17 wherein said olefin polymer comprises polyisobutylene.

19. An additive concentrate which comprises (A) from 10 to 70 weight percent of at least one oil soluble ashless dispersant, (B) from 10 to 40 weight percent of at least one sulfurized alkyl phenol, (C) from 0.5 to 5 weight percent of at least one organo-sulfur compound of the formula

wherein R⁴ and R⁵ are straight or branched chain alkyl, cyclic, alicyclic, aryl, alklaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, and w and z are numbers from 1 to 8, and from 30 to 80 weight percent base oil, the additive concentrate having a total sulfate ash level (SASH) of less than 0.01 weight %.

20. The use of the lubricating composition of claim 1 in a diesel engine in conjunction with a normally liquid fuel having a sulfur content of less than 1 weight percent.

21. The use of the lubricating composition of claim 1 in a diesel engine provided with at least one tight top land piston.

22. The use according to claim 21 wherein said diesel engine is adapted for use in conjunction with a normally liquid fuel having a sulfur content of less than 1 weight percent.

23. The use of the lubricating composition of claim 1 in a diesel engine provided with a lubricating oil crankcase and at least one tight top land piston.

24. The use according to claim 23 wherein said diesel engine is adapted for use in conjunction with a normally liquid fuel having a sulfur content of less than 1 weight percent.